Patent GB-475994-A (GB)
Title: Manufacture of indigoid vat dyestuffs
IPC: C09B7/00
Filed: 1936-12-31
Abstract: Indigoid vat dyestuffs are prepared from oxythionaphthenes or indoxyls having an alkoxyalkoxy group in the isocyclic nucleus either by oxidation or by condensing them or their reactive 2-derivatives with suitable indigoid components.  In examples: (1) 5-(or 6-)methoxyethoxy - 3 - oxythionaphthene is oxidized by means of an aqueous suspension of sulphur; (2) 6-methoxyethoxy-3-oxythionaphthene is condensed with 3-oxythionaphthene-2-b  - dimethylaminoanil, 5 : 7 - dichlorisatinchloride, 5 : 7-dibromisatinchloride, 5-chlor-7-methyl - 3 - oxythionaphthene - 2 - p - dimethylaminoanil and 6-ethoxy-3-oxythionaphthene; (2) 5-methoxyethoxyisatinchloride is condensed with 4-methoxy-1-oxynaphthalene and 4 : 6-dimethyl - 7 - brom - 3 - oxythionaphthene; (3) 6 - methoxyethoxy - 3 - oxythionaphthene - 2 - p - dimethyl aminoanil is condensed with 4 : 6-dimethyl - 7 - chlor - 3 - oxythionaphthene; (4) 5-methoxyethoxy-7-chlorisatin chloride, prepared from the parent isatin by means of sulphuryl chloride is condensed with 4-methoxy-1-oxynaphthalene; (5) acetate artificial silk is dyed by means of an emulsion containing sulphite cellulose liquor, soap and the dyestuff obtained from 6 - methoxyethoxy - 3 - oxythionaphthene and 5-chlor-7-methyl-3-oxythionaphthene - 2 - p - dimethylaminoanil; (6) 6 : 6<1>-dimethoxyethoxythioindigo is dissolved in nitrocellulose lacquer which may be applied to metal, glass, leather, wood, celluloid, silk, cotton or paper.  Properties of dyestuffs prepared as follows are tabulated: 5-methoxyethoxy-3-oxythionaphthene condensed with 3-oxythionaphthene-2-p-dimethylaminoanil, 2 : 1-naphthioindoxyl - 2 - p - dimethylaminoanil, 5 : 7-dibromisatinchloride and 5-chlor-7-methyl-3-oxythionaphthene-2 - p - dimethylaminoanil, 5-methoxyethoxy - 3 - oxythionaphthene - 2 - p-dimethylaminoanil condensed with 4 : 6-dimethyl - 5 : 7 - dichlor - 3 - oxythionaphthene and 3-oxythionaphthene, 6-methoxyethoxy-3-oxythionaphthene condensed with 2 : 1-naphoxythionaphthene condensed with 2 : 1-naphththioindoxyl - 2 - p - dimethylaminoanil, 5-bromisatinchloride, 4-methyl-5-chlor-7-methoxyisatinchloride, 4 : 5-dichlor-7-methoxyisatin, 4 : 7-dimethylisatinchloride, 4-chlor-7-methoxyisatinchloride, 6-amino-3-oxythionaphthene-2-p-dimethylaminoanil, 6-chlor-5-methyl-3-oxythionaphthene - 2 - p - dimethylaminoanil, and 2 - naphththioindoxyl - 2 - p - dimethylaminoanil, 6 - methoxyethoxy - 3 - oxythionaphthene - 2 - p-dimethyl aminoanil condensed with 4 : 6-dimethyl - 7 - brom - 3 - oxythionaphthene, 4 : 6-dimethyl-5 : 7-dichlor-3-oxythionaphthene and 8 - chlor - 1 : 2 - naphththioindoxyl, 5 - methoxy-ethoxyisatinchloride condensed with 6-methoxy-ethoxy - 3 - oxythionaphthene, 4 - chlor - 1-oxynaphthalene, 3-oxythionaphthene and 4 : 6-dimethyl-5 : 7-dichlor-3-oxythionaphthene, 5-methoxyethoxyisatin condensed with 3-oxy-thionaphthene-2-carboxylic acid or 3-oxythionaphthene, 5 - methoxyethoxy - 7 - chlorisatinchloride condensed with 4-chlor (or benzoyl)-1-oxynaphthalene, the chloride of 5-methoxy-ethoxy-7-bromisatin (prepared by bromination of the parent isatin) condensed with 4-brom-1-oxynaphthalene, 5-ethoxyethoxyisatin chloride condensed with 4-methoxy-1-oxynaphthalene, 1-oxynaphthalene and 6-methoxyethoxy (and 6-ethoxyethoxy) - 3 - oxythionaphthene, 6-ethoxyethoxy-3-oxythionaphthene condensed with 5-methoxyethoxyisatinchloride, 6-ethoxy-3 - oxythionaphthene - 2 - p - dimethylaminoanil, 6 - ethoxyethoxy - 3 - oxythionaphthene - 2 - p - dimethylaminoanil, 5 - chlor - 7 - methyl - 3 - oxythionaphthene - 2 - p - dimethylaminoanil and 6 - amino - 3 - oxythionaphthene - 2 - p - dimethylaminoanil, 6 - ethoxyethoxy - 3 - oxythionaphthene - 2 - p - dimethylaminoanil condensed with 4 : 6-dimethyl-5 : 7-dichlor-3-oxythionaphthene, 4 - methyl - 5 - chlor - 7 - methoxyethoxyisatin - 2 - chloride condensed with 4-methoxy-1-oxynaphthalene, the chloride of 4-methyl-5-brom-7-methoxyethoxyisatin (obtained by bromination in glacialacetic acid of the parent isatin) condensed with 4-methoxy-1-oxynaphthalene and 4-brom (or chlor) - 1 - oxynaphthalene, 4-methoxyethoxy - 5 - brom - 7 - methyl isatin-2-chloride condensed with 4-methoxy-1-oxynaphthalene.  5 - Methoxyethoxy-3-oxythionaphthene is prepared from 4-nitro-1-phenol by forming 1-methoxyethoxy-4-nitrobenzene by treatment with the toluene sulphonic acid ester of glycolmonomethylether, reducing, diazotizing the 1-methoxyethoxy - 4 - aminobenzene, reacting with potassium xanthate, saponifying and condensing with chloracetic acid to form the thioglycollic acid and effecting ring closure of the latter by means of phosphorus trichloride and aluminium chloride. 6-Methoxyethoxy-3-oxythionaphthene is prepared from 4-methoxyethoxy-1-aminobenzene hydrochloride by the Herz method. The 4 - methoxyethoxy - 1 : 2 - phenylene thiazothionium chloride obtained by treatment with sulphur chloride is saponified and condensed with chloracetic acid.  The resulting thioglycollic acid anhydride is diazotized and reacted with copper cyanide and 6-methoxyethoxy-3-oxythionaphthene obtained by ring closure.  6 - Ethoxyethoxy - 3 - oxythionaphthene is similarly obtained from 1-ethoxyethoxy-4-aminobenzene which may be prepared from 4-nitrophenol by condensing with p-toluene sulphonic acid ester of glycolmonoethylether and reducing.  5-Ethoxyethoxyisatin is prepared by Sandmeyer's method from 1-ethoxyethoxy-4-amino-benzene by reacting with chloralhydrate and hydroxylamine and saponifying the product with sulphuric acid. 4-Methyl-5-chlor-7-methoxyethoxyisatin is prepared by chlorinating with sulphuryl chloride, the isatin obtained by Sandmeyer's method from 1-methoxyethoxy-2-amino-4-methylbenzene, which may be obtained from 1-oxy-2-nitro-4-methylbenzene by reacting with the p-toluenesulphonic acid ester of glycolmonomethylether and reduction.  4-Methoxyethoxy - 5 - brom - 7 - methylisatin is obtained by bromination of the parent isatin which is derived by Sandmeyer's method from 1 - methoxyethoxy - 3 - amino - 4 - methylbenzene.  The latter is obtained from 1-oxy-3-nitro-4-methylbenzene by condensing with the p-toluene sulphonic acid ester of glycolmonomethylether and reducing. 5-Methoxyethoxyisatin is obtained from 1-methoxyethoxy-4-aminobenzene by Sandmeyer's method.